N-trinitroalkyl-n-nitroaminoalkyl acids and derivatives thereof



United States 3,007,960 Patented Nov. 7, 1961 free 3,007,960 N-TRINITROALKYL-N-NITROAMINOALKYL ACIDS AND DERIVATIVES THEREOF Henry Feuer, Lafayette, Ind., and Charles R. Koller,

Wilmington, Del., assignors to Purdue Research Foundation, a corporation of Indiana No Drawing. Filed Nov. 10, 1958, Ser. No. 777,533 27 Claims. (Cl. 260-482) Our invention relates to novel nitro compounds and more particularly it relates to N-trinitroalkyl-N-nitroaminoalkyl acids, derivatives thereof and to a process for producing same.

Compounds such as ethyl N-(2,2,2-trinitroethyl)glycine are known to the art but are highly unstable and decompose rapidly at room temperature to form nitroform. Furthermore, the compounds cannot be hydrolyzed to form the acid without vigorous decomposition. For these reasons, this type of compound has found little utility in either the explosive or rocket propellant industry.

We have now discovered that the nitramines of trinitroalkyl substituted compounds are quite stable and can be hydrolyzed to the acid form. Polymers having utility as rocket propellants and explosives can easily be prepared trom these trinitro nitramine acids.

Our new compounds are represented by the following structural formula:

R3 where R is selected from the group consisting of hydrogen and alkyl having up to five carbon atoms; R is the radical N02 -l I-R O (N02); R is selected trom the group consisting of the radicals and lower alkylene; R is selected from the group consisting of the radicals R is selected from the group consisting of a hydroxyl radical, an alkoxyl radical having up to five carbon atoms and halo; R is alkylene having up to ten carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, R substituted alkyl having up to five carbon atoms, hydroxy substituted alkyl having up to five carbon atoms, R and hydroxy substituted alkyl having up to five carbon atoms, and R and R substituted 'alkyl having up to five carbon atoms; and n is anin-teger between 3 and 9.

Compounds within the scope of the above formula include ethyl N-trinitroethyl-N-nitroglycine, N-trinitroethyl-N-nitroglycine, N-trinitroethyl-N-nitroglycyl chloride, N-trinitropropyl-N-nitroglycine,

methyl N-t1initroethyl-N-nitro-/8-alanine, ethyl N-trinitroethyl-N-nitro-fi-alanine, N-trinitroethyl-N-nitro-fi-alanine, N-trinitroethyl-N-nitro-fi-alanyl chloride, N-trinitroethyl-N-nitro-fi-alanyl bromide,

diethyl N-trinitroethyl-N-nitroaspartate,

N-trinitroethyl-N-nitroaspartic acid,

N-trinitroethyl-N-nitroaspartyl chloride,

dimethyl N-trinitroethyl-N-nitroglutamate,

diethyl N-trinitroethyl-N-nitroglutamate,

N-trinitroethyl-N-nitroglutamic acid,

N-trinitroethyl-N-nitroglutamyl chloride,

diethyl-e- (N-trinitroethyl-N-nitroamino glutarate,

3-(N-trinitroethyl-N-nitroamino)glutaric acid,

B-(N-trinitroethyl-N-nitroamino) glutaryl chloride,

diethyl ,8-(N-trinitroethyl-N-nitroamino) adipate,

8-(N-t'1initroethyl-N-nitroamino) adipic acid,

B-(N-trini-troethyl-N-nitroamino)adipyl chloride,

,8- (N trinitropropyl-N-nitroamino) adipyl bromide,

N-2- l-trinitromethylbutyl -N-nitro-2-aminocaproic acid,

N-2-( l-trinit-romethylpentyl) -N-nitro-2-aminovaleric acid,

N- 2,2,2-trinitroethyl N-nitro-Z-arninocaproic acid,

N 2,2,2-trinitroethyl)-N-nitno-2-amino-3-ethyl-butyric act ethyl N (2,2,2 trinitroethyl)-N-nitro-4-amino-2,2-dimet-hylbuty ratc,

N- 2,2,2-trinitroethyl) -N-nitro-4-aiminoenanthic acid,

N (l-tn'nitromethylbutyl) -N-nitro-3 amino-2,6-dimethylcaprylic acid,

ethyl 2 nitrate 3-[N-nit-ro-N-(1-phenyl-2,2,2-trinitroethyl) amino] l -propionate,

butyl 2 [N-nit-ro N-(1-cyolohexyl-Z,2,2-trinitroethyl)- amino] -3 -nitrato-propionate,

2,6 bis[N-nitro N-(cyclopentyl-Z,2,2-trinitroethyl)amino]-1-hexanoic acid,

pentyl 2,3 bisEN nitro-N-(1-cyclooctyl-2,2,2-trinitroethyDaminolbutyrate,

2 methyl 2-[N-nitro-N-(1-m-nlitrophenyl-2,2,2-t1initr0- ethyl) amino] propionyl iodide,

propyl 4- E-N-nitno-( 1-p-chlorophenyl-2,2,2-trinitroethyl) aminolheptanoate,

l0 [N-nitro-N-(2,2,2-trinitroethyl)amino] decanoic acid,

3,7 bisEN nitro-N-(2,2,2-trinitroethyl)arnino]-1,8-octanedioic acid,

2,5 bisEN nitro-N(1-tolyl-2,2,2-trinitroethy1)amino]- 1,6hexanedioic acid, etc.

The series of reactions which lead to the trinitro substituted nitramine compounds of our invention are indicated by the following sequence of reactions, with glycine as an example:

(OzNhC-GHgNHCHzOOiCzHri-H O Generally our process consists of reacting a trinitro substituted alcohol having the following structural formula:

I-IO-R -C (N0 3 with an amino acid ester having the structural formula:

w RC-R where R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, primary amine substituted alkyl having up to five carbon atoms, hydroxy substituted alkyl having up to five carbon atoms, primary amine and hydroxy substituted alkyl having up to five carbon atoms, and primary amine and carboxyl substituted 'alkyl having up to five carbon atoms; and R is selected from the group consisting of the radicals and I! -R o-R and R is an alkoxy radical having up to five carbon atoms, and n is an integer between 3 and 9 to obtain an N-trinitroalkylamino ester. The latter compound is then nitrated to obtain the corresponding N-nitro ester which upon hydrolysis yields the corresponding free acid. The free acid is in turn converted to the acid halide by reacting the free acid with a thionyl halide, a phosphorus pentahalide, a phosphorus trihalide, etc.

Hydroxy substituted amino acids can also be utilized in our process, in which case, the nitrate free acid is obtained by hydrolyzing the N-nitro-N-trinitro substituted nitrato ester with nitric acid.

As indicated above, the first step in our process is concerned with the reaction of a trinitroalkyl alcohol with an alkylamino acid ester. The trinitroalkyl alcohol can be employed as such or it can be produced in situ by the reaction of nitroform with an aldehyde such as formaldehyde, acetaldehyde, etc. We prefer to produce the trinitroalkyl alcohol in situ by reacting nitroform and the desired aldehyde at low temperatures and in aqueous solution. The reaction between the trinitro'alkyl alcohol and the alkylamino acid ester is carried out in the presence of a base. Suitable bases include alkali metal hydroxides, alkaline earth metal hydroxides, etc. The reaction is also carried out preferably at low temperatures within the range to 25 (3., however higher temperatures can be employed' Thus, using ethyl glycine and trinitroethanol as examples, we can react the two mate rials in the presence of sodium hydroxide at a temperature of about C. to obtain ethyl N-trinitroethylglycine. Upon completion of the reaction, the reaction mixture separates into two phases and the oily product layer can be separated from the aqueous layer by any convenient means such as for example, decantationl In some instances, as in the case of ethyl N-trinitroethylglycine, the oily product layer solidifies so that the trinitroalkylamino acid esters can be obtained in dry, solid form. Usually, however, the oily layer does not solidify and in such instances it is generally desirable to dry the same by any convenient means, for example, dissolving the oily layer in ether, adding magnesium sulfate as a drying agent,

removing the drying agent, and then removing the ether by distillation.

The second step in our new process is concerned with the nitration of the trinitroalkylamino acid ester to obtain the corresponding N-nitro compound. The nitration is carried out using nitric acid as the nitrating agent, generally in the form of a nitrating mix with sulfuric acid, acetic anhydride or other acidic dehydrating agent. Generally we prefer to carry out the nitration reaction at a. temperature ranging from about 5 to 25 C. Temperatures as high as about.50 to 60 .C, can be employed but as indicated, we prefer to employ temperatures considerably below this level. Following completion of the nitration reaction, we can'generally obtain the N-nitro- N-trinitroalkylamino acid ester as a solid by cooling the reaction mixture to a temperature of about 0 or below.

as by pouring the reaction mixture over ice. The resultin nitric acid and again cooling to the low temperatures the equilibrium toward maximum production of the free acid. In some instances, it is desirable to thoroughly free the ester of nitric acid as, for example, where the N-nitro compound is not obtained in crystalline or otherwise solid form. The N-nitro-N-trinitroethylamino acids can ordinarily be recovered from the reaction mixture by cooling to crystallize or by concentrating and cooling to crystallize the free acid product. In some instances, however, it is necessary to dry the reaction mixture in vacuo, dissolve the residue in a suitable solvent such as, for example, ether and then crystallize the same by addition of hexane or other suitable material to the ether solution. Ordinarily, the acid product can be recrystallized from ethylene dichloride or other similar solvents.

The final step in our new process is concerned with theconversion ofthe N-nitro-N-trinitroalkylamino acid to the corresponding acid halide. In this step of our process, we react the N-nitro-N-trinitroalkylamino acid with a halogenating agent suchas thionyl chloride, phosphorus pentachloride, phosphorus trichloride, thionyl bromide, etc. The reaction is generally conducted under conditions of elevated temperatures, preferably 40 to 50 C., although in some instances it is necessary to reflux the reactants in order to obtain the desired product. Following the reaction, the excess halogenating agent is removed by distillation as in the case of thionyl chloride or other convenient means leaving a residual oil which can generally be crystallized by addition of a hydrocarbon solvent such as hexane or a higher hydrocarbon solvent or mixture thereof. In some instances, the acid chloride can be crystallized by concentration and cooling of the' product oil. Generally, the acid chloride can be recrystallized from carbon tetrachloride or other suitable solvent. 0

Our monomers can be used as liquid propellants or can be utilized to form polymers useful in both'solid and liquid propellants for reaction motors. These polymers can be fluids or solids, dependingupon the chain length of the polymer, the nature of the cross-linking agent, etc. These polymers are also stable to shock, heat, etc. to the extent that, as a general rule, additional stabilizers are not required in the propellant mixtures. j, V a

Our oily monomers are generally rich in fuel elements and as such can be utilized as a fuel in the process of US. Patent 2,537,526 where tetranitromethane and hexanitroethane were used as'oxidants'and liquid nitroparaffins were used as fuels; in the processes described in US.

Patents 2,582,048 and 2,548,803 wherein nitro'substinitroalkanes, such as tetranitromethane, and, as such,

are operative as fuels in the above-described processes. Other solvents which can be usedito liquify our polymers include dimethylsulfoxide, Cellosolve, acetonitrile, lower alkanols, nitro. esters andn'itro ethers. Straight chain polymers can be formedby reaction of our dicarboxylic acid esters, acids, and halides with dihydroxy' alcohols,

such as ethylene glycol,,1,3-butylene glycol, LG-hexane:

diol, 2,2-dinitro-1,3 propanediol, etc; For example, N-

nitro-N-tiinitroethylaspartic acid combines with ethylene 7 Example VII By a process similar to the process of Example I, ethyl R Ir -LE1 3 Where R is selected from the group consisting of hydrogen and alkyl having up to five carbon atoms; R is the radical 1:102 N-R2C (N093 R is selected from the group consisting of the radicals A OH2)uCHCH- and lower alkylene; R is selected from the group con sisting of the radicals and R is selected from the group consisting of a hydroxyl radical, halo, and an alkoxyl radical having up to five carbon atoms; R is alkylene having up to ten carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, R substituted alkyl having up to five carbon atoms, hydroxy substituted alkyl having up to five carbon atoms, and R and R substituted alkyl having up to five carbon atoms, and n is an integer between 3 and 9.

2. N-trinitroethyl-N-nitroglycine. 3. Ethyl N-trinitroethyl-N-nitroglycine. 4. N-nitro-N-trinitroethyl- -alanine. 5. N-nitro-N-trinitroethylaspartic acid. 6. N-trinitroethyl-N-nitroglutamyl chloride.

7. The process which comprises contacting a trinitroalkyl alcohol having the structural formula:

HO-R C(NO 3 where R is selected from the group consisting of the radicals and lower alkylene with an amino acid ester having the structural formula:

and alkyl having up to five carbon atoms; R is alkylene having up to ten carbon atoms; R is selected from the group consisting of hydrogen, alkyl having up to five carbon atoms, primary amine substituted alkyl having up to five carbon atoms, hydroxy substituted alkyl having up to five carbon atoms, primary amine and hydroxy substituted alkyl having up to five carbon atoms, and primary amine and carboxyl substituted alkyl having up to five carbon atoms, and R is selected from the group consisting of the radicals R is an alkoxy radical having up to five carbon atoms, and n is an integer between 3 and 9 in the presence of a base to obtain an N-trinitro substituted amino ester and contacting fuming nitric acid with the latter com! pound in the presence of an acidic dehydrating agent to obtain a trinitro substituted nitramino ester.

8. The process of claim 7 wherein the final product of claim 7 is contacted with an acid to obtain the corresponding free acid.

9. The process of claim 7 wherein the compound of claim 8 is contacted with an acid to obtain the free trinitro substituted nitramino acid which is then contacted with a compound selected from the group consisting of thionyl halide, phosphorus pentahalide and a phosphorous trihalide to obtain the corresponding trinitro substituted nitramino acid halide.

10. The process which comprises contacting trinitroethanol with ethylglycine in the presence of a base to obtain ethyl N-trinitroethylglycine and contacting fuming nitric acid with ethyl N-trinitroethylglycine to obtain ethyl N-nitro-N-trinitroethy1glycine.

11. The process which comprises contacting trinitroethanol with ethylglycine in the presence of a base to obtain ethyl N-trinitroethylglycine, contacting fuming nitric acid with ethyl N-trinitroethylglycine to obtain ethyl N-nitro-N-trinitroethylglycine, and contacting an acid with ethyl N-nitro-N-trinitroethylglycine to obtain N-nitro-N-trinitroethylglycine.

12. The process which comprises contacting trinitroethanol with ethylglycine in the presence of a base to obtain ethyl N-trinitroethylglycine, contacting fuming nitric acid with ethyl N-trinitroethylglycine to obtain ethyl N-nitro-N-trinitroethylglycine, contacting an acid with ethyl N-nitro-N-trinitroethylglycine to obtain N-nitro-N-trinitroethylglycine, and contacting N-nitro-N-trinitroethylglycine with a compound selected from the group consisting of thionyl chloride, phosphorus pentachloride, and phosphorus trichloride to obtain N-nitr0-N- trinitroethylglycyl chloride.

13. The process which comprises contacting trinitroethanol with ethyl fi-alanine in the presence of a base to obtain ethyl N-trinitroethyl-B-alanine, and contacting fuming nitric acid with ethyl N-trinitroethyl-fl-alanine to obtain ethyl N-nitro-N-trinitroethyl-fl-alanine.

14. The process which comprises contacting trinitroethanol with ethyl fi-alanine in the presence of a base to obtain ethyl N-trinitroethyl o-alanine, contacting fuming nitric acid with ethyl N-trinitroethyl-B-alanine to obtain ethyl N-nitro-N-trinitroethyl-p-alanine, and contacting an acid with ethyl N-nitro-N-trinitroethyl-fi-alanine to obtain N-nitro-N-trinitroethyl-B-alanine.

15. The process which comprises contacting trinitroethanol with ethyl fi-alanine in the presence of a base to obtain ethyl N-trinitroethyl-B-alanine, contacting fuming nitric acid with ethyl N-trinitroethyl-fi-alanine to obtain ethyl N-nitro-N-trinitroethyl-B-alanine, contacting an acid with ethyl N-nitro-N-trinitroethyl-B-alanine to obtain N-nitro-N-trinitroethyl-fi-alanine, and contacting N- nitro-N-trinitroethyl-fl-alanine with a compound selected from the group consisting of thionyl chloride, phosphorus a lycol toyield a polymer having the following structural ormula:

vherein n is an integer.

This particular polyester plastic was found to have a pecific impulse of 215 indicating that this polymer could e used as a solid propellant substitute for compositions uch as Ballistite. Other polymers utilizing dibasic acids an be formed from N-nitro-N-trinitroethylglutamic acid nd ethylene glycol. Such a plastic prepared from a 1:1 atio of acid .to alcohol was found to have a specific imu1se of 204. Other polymers utilizing the monocarboxlic acid compounds of our invention can be easily, preared by reacting two moles of a compound such as J-trinitroethyl-N-nitroglycine with one mole each of xalic acid and glycerol. Other polymer can be prepared y reacting similar compounds with varying ratios or nixtures of dicarboxylic acids and glycols or .glycerols.

Our monomers form rubber-like materials with varirusdiisocyanatecross-linking agents.

Our polymers can be mixed with various oxidant salts, uch as ammonium nitrate, ammonium perchlorate, lithum perchlorate, etc. to obtain solid heterogeneous prouellants having specific impulses on the order of that of lallistite. V

The following examples are olferedto illustrate our nvention; however, we do not intend to'be limited to he specific portions, procedures, and materials described. Kather, we intend to include within the scope of our inentidn allequivalents obvious to those skilled in the art.

Example I To a mixture of 7.24 grams of trinitroethanol and 5 .6 grams of ethylglycine hydrochloride in 50 ml. of water vas slowly added 8 ml. of 5 N sodium hydroxide while he temperature was maintained at about 20 C. The olution was stirred for 15 minutes at 20 and an oil sepaated which solidified to a light yellow solid when the olution was allowed to stand at 5? for 30 minutes. The olid was filtered, washed with cold water and dried to btain 6.7 grams of ethyl N-trinitroethylglycine. M.P. 16-119 C., The ethyl N-trinitroethylglycine wasadded oanitratirig-mixture prepared by mixing 10 ml. of fumhg nitric ,acidwith 10 ml. of concentrated sulfuric acid, he mixturewas stirred at a temperature of 25f C. and hen poured onto 5 OOJgrafns of ice toprec'ipitate a white olid whichwa s washed with water and dried in a vacuum lesiccator to obtain 5.68 grams of ethyl N-trinitroethyl -I-nitroglycine. The material 'was recrystallized from :arbon tetrachloride. M.P. 78 C.' To 9.7 grams of ethyl -I-trinitroethyl-N nitroglycine was added 100 ml; of conentrated (38 hydrochloric acid and the suspension leated at slow, reflux for 24 hours. The solution was then :oo-led to C. to crystallize a'white solid which wa's iltered off and dried. The dryma'te'rial wasrecrystalized from ethylenedichloride to obtain 7 grams of N- rinitroethyl-N-nitroglycine having a melting point of i49. C with decomposition. Analysis: Calculated -I='24.73. 'Fou'nd N =24.5%. One gram of N trinitro- -.thyl-N-nitroglycine was suspended in 15 ml. ofthionyl :hloride and heated atreflux for four hours. Theremain ng thionyl chloride was then :distilled off and the residual il crystallized upon additionof 35 ml. of a mixture of ligher'hydrocarbons' identified 'as Skellysolve B. 'The vhite solidwas filtered ofit, washed with Skellysolve B and he excess solvent removed in vacuo at 25 C. to obtain L85 gram of N-trinitroethyl-N nitroglycyl chloride. M.P. l82 C. Analysis: Calculated N=23.22%. Found \I=23.38%.

A solution of 71. grams of diethylglutamate hydrochlo- 6. ride, 45 grams of nitroform,.24.'5 m1. of 37% formalin solution in 300 ml. of distilled water was stirred at 5 C. and approximately 60 ml. of 5 vN sodium hydroxide added to the solution in 20 minutes. The-mixture was stirred at 5 to 10 C. for another minutes and then'allowed to stand at that temperature for 1 hourafter which the water was decanted and the oily diethyl N-trinitroethylglutamate dissolved in about 150 ml. of ether. 1 This solution wasthen dried with magnesium :sulfateand the solvent removed in vacuo. The remaining oil was dissolved in 70 m-L-of acetic .anhydride, cooledto 5 Crand ml. of fumingnitric acid'added over'a periodof 1 /2 hours while the temperature was maintained at 5' to -15- C. After theaddition had been completed, thenitratiorr mixture was stirred at 25 C. for onehour and then poured over crushed ice to pecipitate an oil which solidified upon standing in the refrigerator. The solid was purified by solution in 25 ml.'of fuming nitric acid followed by precipitation over cracked ice to obtain 88.8 grams of diethyl N-nitro-N-trinitroethylg'lntamate. -M.P. -51-52 C. Twenty grams of diethyl N.-trinitroethyl Nenitroglutamate was suspended in a mixture of 160 ml. ofconcentrated hydrochloric acid and 40 ml. of Water, and heated at reflux for 22 hours. The resultingsolution was concentrated to 75 ml., cooledto' 0 C; to crystallize a light yellow solid which, was dried, recrystallized from ethylene dichloride to obtain N trinitroethyl-N-nitroglutamic acid. M.P. 127-128 C. with decomposition. Analysis: Calculated N=19.71% Found N=19.78%. A 1.7 grams portions of the N-trinitroethyl-N-nitroglutamic acid and 2.1 grams of phosphorus pentachloride were combined. A vigorous evolutionof hydrogen chloride began within five minutes and the flask was'cooledjto'moderate the reaction. The mixture was then allowed *to stand at 25 C. until a homogeneous liquid resulted in 72 hours. To the solution, 35 ml. of carbon tetrachloride was added and'a small amount of insoluble material filtered from the solution. After distilling the carbon tetrachloride, the

residual oil was heated-for one hour at 30 C. and 1 mm.

mercury in order to remove the phosphorus oxychlo-n'de. To the residue was added 40 ml. of Skellysolve B and the oil solidified to a white solid which was filtered, washed and dried in vacuo at 25 C. to obtain 13' grams of N-trinitroethyl-N-nitroglutamyl chloride. M.P. 7l72 C. Analysisz'Calculated N: 17.85% Found N: 17.81%

Example III By a process similar to that described above, ethyl fl-alanine hydrochloride was converted to ethyl N-trinitroethyl ,B-alanine, then to ethyl N-nitro-N-trinitroethyl fl-alanine, then to N-nitro-N-trinitroethyl fl-alanine, and

Exam p'l e V V 'By a process similar to that described above'diethyl B-amino glutarate hydrochloride was converted to diethyl B-(N-trinitroethylamino)glutarate, then to diethyl fl-(N- nitro-N-trinitroethyl-amino)glutarate,then to B-(N-nitro- N-trinitroethylamino)glutaric acid, and finally to trinitroethylaminmN-nitro)glutaryl chloride .Exnlmp le VI A V A By a process similar to that described. above, diethyl B-aminoadipate hydrochloride Wasconverted to diethyl" B-(N-trinitroethylamino)adipate, then to diethyl 'B-(N nitro-N- trinitroethylamino)adipate, then to B-(N-nitro-N- trinitroethylamino)adipic acid, and finally to [i-(N-nitro- N trinitroethylamino)adipyl chloride; g

pentachloride, and phosphorus trichloride to obtain N- nitro-N-trinitroethyl-,8-alanyl chloride.

16. The process which comprises contacting trinitroethanol with diethyl aspartate in the presence of a base to obtain diethyl N-trinitroethyl-aspartate and contacting fuming nitric acid with diethyl N-trinitroethylaspartate to obtain diethyl N-nitro-N-trinitroethylaspartate.

17. The process which comprises contacting trinitroethanol with diethyl aspartate in the presence of a base to obtain diethyl N-trinitroethylaspartate, contacting fuming nitric acid with diethyl N-trinitroethylaspartate to obtain diethyl N-nitro-N-trinitroethylaspartate, and contacting an acid with diethyl N-nitro-N-trinitroethylaspartate to obtain N-nitro-N-2,2,Z-trinitroethylaspartic acid.

18. The process which comprises contacting trinitroethanol with diethyl aspartate in the presence of a base to obtain diethyl N-trinitroethylaspartate, contacting fuming nitric acid with diethyl N-trinitroethylaspartate to obtain diethyl N-nitro-N-trinitroethylaspartate, contacting an acid with diethyl N-nitro-N-trinitroethylaspartate to obtain N-nitro-N-2,2,2-trinitroethylaspartic acid, and contacting N-nitro-N-2,2,2-trinitroethylaspartic acid with a compound selected from the group consisting of thionyl chloride, phosphorus pentachloride, and phosphorus trichloride to obtain N-nitro-N-trinitroethylaspartyl chloride.

19. The process which comprises contacting trinitroethanol with diethyl glutamate in the presence of a base to obtain diethyl N-trinitroethylglutamate, contacting fuming nitric acid with diethyl N-trinitroethylglutamate to obtain diethyl N-nitro-N-trinitroethylglutamate.

20. The process which comprises contacting trinitroethanol with diethyl glutamate in the presence of a base to obtain diethyl N-trinitroethylglutamate, contacting fuming nitric acid with diethyl N-trinitroethylglutamate to obtain diethyl N-nitro-N-trinitroethylglutamate, contacting an acid with diethyl N-nitro-N-trinitroethylglutamate to obtain N-nitro-N-Z,2,2-trinitroethylglutamic acid.

21. The process which comprises contacting trinitroethanol with diethyl glutamate in the presence of a base to obtain diethyl N-trinitroethylglutamate, contacting fuming nitric acid with diethyl N-trinitroethylglutamate to obtain diethyl N-nitro-N-trinitroethylglutamate, contacting an acid with diethyl N-nitro-N-trinitroethylglutamate to obtain N nitro N-2,2,3-trinitroethylglutamic acid, and contacting N-nitro-N-2,2,2-trinitroethylglutamic acid with a compound selected from the group consisting of thionyl chloride, phosphorus pentachloride, and phosphorus trichloride to obtain N-nitro-N-trinitro-ethylglutamyl chloride.

22. The process which comprises contacting trinitroethanol with diethyl fl-aminoglutarate in the presence of a base to obtain diethyl fi-(N-trinitroethylamino)glutar- '10 ate, contacting fuming nitric acid with diethyl [it-(N-trinitroethylamino)glutarate to obtain diethyl B-(N-nitro- N-trinitroethylamino) glutarate.

23. The process which comprises contacting trinitroethanol with diethyl fl-aminoglutarate in the presence of a base to obtain diethyl fl-(N trinitroethylamino)glutarate, contacting fuming nitric acid with diethyl B-(N-trinitroethylamino)glutarate to obtain diethyl ,B-(N-nitro- N-trinitroethylamino)glutarate, contacting an acid with diethyl [3-(N-nitro-N-trinitroethylamino)glutarate under acid conditions to obtain 8-(N-nitro-N-trinitroethylamino)glutaric acid.

24. The process which comprises contacting trinitroethanol with diethyl fi-aminoglutarate in the presence of a base to obtain diethyl B-(N-trinitroethylamino)glutarate, contacting fuming nitric acid with diethyl fi-(N-trinitroethylamino)glutarate to obtain diethyl ,B-(N-nitro- N-trinitroethylamino)glutarate, contacting an acid with diethyl 8-(N-nitro-N-trinitroethylamino)glutarate to obtain [i-(N-nitro-N-trinitroethylamino)glutaric acid, and contacting 18-(N-nitro-N-trinitroethylarnino)glutaric acid with a compound selected from the group consisting of thionyl chloride, phosphorus pentachloride, and phosphorus trichloride to obtain 8-(N-nitro-N-trinitroethylamino)glutaryl chloride.

25. The process which comprises contacting trinitroethanol with diethyl fi-aminoadipate in the presence of a base to obtain diethyl ,B-(N-trinitroethylamino)adipate, contacting fuming nitric acid with diethyl B-(N-trinitroethylamino)adipate to obtain diethyl ,B-(N-nitro-N-trinitroethylamino) adipate.

26. The process which comprises contacting trinitroethanol with diethyl fi-aminoadipate in the presence of a base to obtain diethyl fl-(N-trinitroethylamino)adipate, contacting fuming nitric acid with diethyl fi-N-trinitroethylamino)adipate to obtain diethyl ,B-(N-nitro-N-trinitroethylamino)adipate, contacting an acid with diethyl ;8-(N-nitro-N-trinitroethylamino)adipate to obtain ,8-(N- nitro-N-trinitroethylamino) adipic acid.

27. The process which comprises contacting trinitroethanol with diethyl B-aminoadipate in the presence of a base to obtain diethyl ,6-(N-trinitroethylamino)adipate, contacting fuming nitric acid with diethyl B-(N-trinitrocthy1amino)adipate to obtain diethyl ,B-(N-nitro-N-trinitroethylamino)adipate, contacting an acid with diethyl fl-(N-nitro-N-trinitroethylamino)adipate to obtain 8-(N- nitro N trinitroethylamino)adipic acid, and contacting fl-(N-nitro-N-trinitroethylamino)adipic acid with a compound selected from the group consisting of thionyl chloride, phosphorus pentachloride, and phosphorus trichloride to obtain fi-(N-nitro-N-trinitroethylamino)adipyl chloride.

No references cited.

UNITED STATES PATENT ermen C SENATE F Patent N00 3 OO'Z 960 November 7 1961 Henry Feuer et al0 It is hereby certified that error appears in the above numbered petent requiring correction and that the said Letters Patent should read as corrected below.

Column 5 line 64 for N 24@5% read N=24LA596 same column 5 between lines "Z4 and 75 insert Example II in italic: as a headings Signed and sealed this lZth day of April 1962,

(SEAL) Attest:

ESTON G, JOHNSON DAVID L. LADD Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N00 35007 960 November 7 1961 Henry Feuer et all:)

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read, as corrected below.

Column 5, line 64 for "N=24e5%"' read N=24a45% same column 5 between lines 74 and 75 insert Example II in italic as a heading.,

Signed and sealed this 17th day of April 196.2e

(SEAL) Attest:

ESTON Go JOHNSON Attesting Officer DAVID L. LADD Commissioner of Patents 

1. THE COMPOSITION HAVING THE FOLLOWING STRUCTURAL FORMULA:
 3. ETHYL N-TRINITROETHYL-N-NITROGLYCINE. 